Patent GB-717889-A (GB)
Title: Improvements relating to fluorescent monotriazole compounds and their use
Filed: 1952-09-04
Abstract: The invention comprises 2-stilbyl-(naphtho11.21:4.5)-1 : 2 : 3-triazolesulphonic acids of the general formula <FORM:0717889/IV (b)/1> (wherein A represents a naphthalene radical which is bound in neighbouring a  : b -positions to the nitrogen atoms of the triazole ring and B represents a radical of the benzene series, and wherein the radicals A and B may contain further substituents other than chromophore or auxochrome groups), and their salts, the preparation thereof by (a) coupling a diazotized 4-aminostilbene - 2 - sulphonic acid with a 1-or 2-aminonaphthalene coupling in the 2- or 1-position respectively and oxidizing the resulting o-aminoazo dyestuff; or (b) diazotizing a 2-(4111-aminostilbyl - 411) - naphtho - 11.21:4.5)-1 : 2 : 3-triazole-211:2111-disulphonic acid and replacing the diazo group by hydrogen by boiling in alcohol or by other substituents by the Sandmeyer process, and the use thereof as optical brightening agents (see Group XL (a)).  Suitable further substituents are halogen atoms, alkyl or alkoxy groups or especially carboxylic or sulphonic acid groups, but the radical B is preferably free from substituents making it strongly positive in ortho- or para-position to the stilbene bridge, and advantageously completely unsubstituted. Suitable starting materials for process (a) are the compounds obtained by condensing aromatic aldehydes of the benzene series with 2-methyl-5-nitrobenzenesulphonic acid aryl esters, saponifying the ester group and reducing the nitro group, or by diazotizing 4 - nitro - 41 - aminostilbene - 2 : 21-disulphonic acid and replacing the diazo group by, for example, hydrogen, halogen or cyanogen.  The oxidation may be effected with ammoniacal copper sulphate (in aqueous solution or suspension at raised temperature), oxygen or mixtures containing it (e.g. air), or alkali metal hypochlorites.  In examples, the following compounds are prepared by method (a) : the sodium salts of 2 - (stilbyl - 411) - (naphtho - 11.21 : 4.5)-1 : 2 : 3 - triazole - 211 - sulphonic acid, - 211 : 41- 211 : 51 -, - 211 : 61 -, - 211 : 71 - and - 211 : 2111-disulphonic acids, - 211 : 31 : 61 -, - 211 : 51 : 71-and - 211 : 2111 : 61 - trisulphonic acids and - 31-carboxylic - 211 - sulphonic acid, 2 - (stilbyl-411) - (61 - and 71 - methoxynaphtho - 11.21 : 4.5)-1 : 2 : 3 - triazole - 211 - sulphonic acids, 2-(4111 - methylstilbyl - 411) - (naphtho - 11.21 : 4.5)-1 : 2 : 3 - triazole - 211 : 51 - and - 211 : 61 - disulphonic acids, 2 - (2111 - and 4111 - chloro -, 2111 : 6111 - dichloro -, 2111 : 4111 - dimethyl-and 2111 - and 4111 - isopropyl - stilbyl - 411) (naphtho - 11.21 : 4.5) - 1 : 2 : 3 - triazole - 211-sulphonic acids, 2 - (2111 - chlorostilbyl - 411)-(naphtho - 11.21 : 4.5) - 1 : 2 : 3 - triazole - 211 : 61-disulphonic acid, and 2 - (4111 - chlorostilbyl-411) - (naphtho - 11.21 : 4.5) - 1 : 2 : 3 - triazole-211 : 2111 - disulphonic acid and - 211 : 2111 : 61-trisulphonic acid and the bromine analogue of the latter; and the following by method (b) : the sodium salts of 2 - (stilbyl p  - 411) - (naphtho11.21 : 4.5) - 1 : 2 : 3 - triazole - 211: 2111 : 61 - and - 211 : 2111 : 41 - trisulphonic acids and their 4111-chloro derivatives.  Specifications 503,576 and 668,199 are referred to.ALSO:Optical brightening of materials is effected by applying a liquor containing a 2-stilbyl-(naphtho-11.21:4.5)-1:2:3-triazolesulphonic acid of the general formula:  <FORM:0717889/IV(c)/1> (wherein A represents a naphthalene radical which is bound in neighbouring a :b -positions to the nitrogen atoms of the triazole ring and B represents a radical of the benzene series, and wherein the radicals A and B may contain further substituents other than chromophore or auxochrome groups), or a salt thereof. These compounds may be applied to cellulosic materials (e.g. cellulose fibres and textiles made therefrom, or paper) as an aqueous solution of an alkali metal salt, or to wool and nylon (in some cases from an acid bath).  In examples: (15) cotton poplin is treated at 40 DEG C. with an aqueous solution of the sodium salt of 2-(stilbyl-4") - (naphtho-11.21:4.5) -1:2:3-triazole-2":6\sF-disulphonic acid and Glauber salt; (16) and (18) white household goods are washed at 90-100 DEG C. with a liquor containing curd soap, soda and the brightening agent of (15); (19) previously bleached wool yarn is treated at 50-60 DEG C. with an aqueous solution of the sodium salt of 2-(stilbyl-4")-(naphtho-11.21:4.5) -1:2:3-triazole-211-sulphonic acid and Glauber salt; (20) nylon is treated at 80-90 DEG C. with an aqueous solution of the brightening agent of (19).  Azo dyes.-In the manufacture of the triazoles formulated above, there are first prepared o-aminoazo dyestuffs by coupling a diazotized 4-aminostilbene-2-sulphonic acid with a 1- or 2-aminonaphthalene coupling in the 2- or 1- position respectively, the components optionally containing further substituents other than chromophore or auxochrome groups.  The following components are employed in examples: 4-aminostilbene-2-sulphonic acid and its 21- and 41- chloro, 21:61-dichloro, 41-methyl, 21:41-dimethyl and 21- and 41-isopropyl derivatives, and 4-aminostilbene-2:21-disulphonic acid and its 41-chloro and 41-bromo derivatives; 2-aminonaphthalene and its 5- and 6-sulphonic acids, 3:6- and 5:7-disulphonic acids and 3-carboxylic acid, 2-amino-6- and 7-methoxynaphthalene and 1-aminonaphthalene-4-sulphonic acid. Specifications 503,576 and 668,199, [Group IV(b)], are referred to.ALSO:Soaps and synthetic washing agents have added thereto as optical brightening agent a small percentage of a 2-stilbyl-(naphtho-11.21 : 4.5)-1 : 2 : 3-triazolesulphonic acid of the general formula <FORM:0717889/III/1> (wherein A represents a naphthalene radical which is bound in neighbouring a  : b -positions to the nitrogen atoms of the triazole ring and B represents a radical of the benzene series, and wherein the radicals A and B may contain further substituents other than chromophore or auxochrome groups), or a salt thereof. In an example, curd soap is homogeneously mixed with the sodium salt of 2-(stilbyl-411)-(naphtho-11.21 : 4.5)-1 : 2 : 3-triazole-211 : 61-disulphonic acid. Specifications 503,576, [Group IV], and 668,199, [Group IV (b)], are referred to.